Process for making condensation products from phenols and formaldehyde.



: rran sax rns PATENT. curios.

nunwro 13:13am), or ArroNE Une-on rHE-BHINE, GERMANY.

PROCESS FOR MAKING CQNDENSATION PRODUGTQ FROM PHENOIS AND FORMAL-DEHYDE.

1,191,390. No Drawing.

To all whom it may concern:

Be it known that L LUDWIG "Bram -11), chemist, citizen of Germany,subject of the Kin of Prussia and Emperor of Germany,

resi 'ng, at Landgrabenweg 14, Amoneburgon-the-Rhine, in the Kingdom ofPrussia and Empire of Germany, have inventedmew and useful Improvementsin Processes for Making Condensation Products from Phenols andFormaldehyde, lowingis a specification.

The present invention relates to a process for making condensationproducts soluble in fatty oils from phenols and formaldehyde andessentially consists in adding an agent transmitting dissolvingqualities" or acting as an intermediary for producing solution to thestill fusible and still soluble phenol resins, which agent is solubleboth in the obtained condensation products and in the fatty-oils. Assuch agents transmitting dis solving qualities for the present purposesresins and resin compounds of all kinds, resin esters, resin acids andtheir salts, the so called resinates, and others are suited. The

of which the folj use of agents transmitting dissolving qualities-initself is already known 'in so far as for instance alcohol is used inorder to render essential oils soluble in water; but in thiscase thesolubility obtained between the heterogeneous components, oil ,andwater, 18 7 I a very limited one. Moreover the conditions are,considerably difierent in so far as the intermediary agent alcohol is asolvent as well for essential oils as also for water,

whereas the-solid resins cannot be considered for resins.

as solvents for the condensation products from phenols and formaldehyde,and still less as a solvent for oils. only the oils can be considered assolvents Moreover'the effect 'here obtained in so far considerablysurpasses that obtained by the mentioned addition of alcohol as thesolubility of-the produced resins in atty oils is an unlimited one;

It has been proposed to. also produce resins which under, certainconditions are soluble kinds,

in oils by the condensation-ofphenols with formaldehyde whenv using tarsof variousbalsams and resins as a catalytic medium.- But I have furtherfound, that ifis, balsams or similar materials are used,

which are soluble as well ktheTformed catalytic medium. If, forinstance, a resin Specification of Letters Patent; Patented Julyis 1916,Application filed December 8,1918. Serial No. 805,365.

is employed in only so small a quantity as is usual for a catalyticmedium for starting a reaction, such as for example 'a quantity ofabout-5% of the employed phenol, a product.

will be obtained which will indeed be soluble during the initial part ofthe reaction, which, however, becomes insoluble in oils on' beingfurtherheated. It had, thus, hitherto not been recognized what part the addedresins and the like play, and that by their action as a catalytic mediumthe solubility ofthe obtained products in oil is not secured.

Neither has the production of resins soluble in oil by er means beenhitherto men tioned, and it could not be expected, that thephenolaldehyde resins hitherto known, which are all insoluble in fattyand essential oils, would become soluble" in oil by being meltedtogether with Oil-soluble resins and similar substances. By this eminenttechnical efi'ec't it will now be possible, to employ the extremelyhard, strong and highly antiseptic phenol formaldehyde-resins 'in a verywide manner, what was heretofore impossible, as now they can easily beworked into The oil-soluble resins" varnishes of all kinds. obtained:are also soluble in oil of turpentine, benzol, benzin and a number ofother known solvents, particularly When they had been previouslyintroduced into the fatty oils.

At the same time the present process allows of rendering harmless theremainder of phenol tenaciously adhering to the fusible On the contrary..andsoluble phenol aldehyde resins by con-- verting them by heatingduring some time with'resin acids into the respective odorless esters,which are likewise readily solublein oil. a

The agents acting as an intermediary for also mixtures of the producingsolution are chosen accordingto the desired purpose;

variousresins, balsams, terpene compounds, 4

waxes, fatty oils and the like maybe used in this sense. Preferably theresins orthe like required for producing the solubility of the productsto be obtained are introduced directly into the reaction mixtures, sothat media and on the other as intermediaries for they are acting on theone hand ascatalytic l I nishesproducing solution. They may, however,

also be fused together with the different intermediate products ofreaction and be thenfurther heated with them, so as tore? move volatileparts, if any.- On the other hand "also the finishedphenol-aldehyde-resins may be fused together with the agents acting asan intermediary for producing solution. r

I have further found that soluble and fusiblephenol-formaldehyde-resins, and preferably such, which have alreadybecome oil-soluble by the present process, are ,excellent solvents forcopals and that sald copals are thereby likewise made readily soluble inoil, without their being previously melted out, as hitherto necessary,and

freed of the volatile acidcopal oils, so that they could be made up infatty OllS to'var- As phenols for the production of the phe nol-resinsall phenols in the farthest sense can be used; so also cre'sols,naphthols, and

their derivates, their halogen compounds,

their carboxylic acids and the like may be used for producing the phenolresins, and place of the formaldehyde its polymeres, tr1- oxymethylene,hexamethylenetet'ramin and other aldehydes may be employed.

I Examples.

1. 100 grams of pure carbolic acid of commerce and 100 grams turpentineresin are heated for 6' hours with 30 grams trioxymethylene in a vesselwith a return condenser to a temperature of 115 to 120 cent. The

' temperature is then, while the mixture is be- 111g stirred,graduallyraised to 200 cent,

in a vessel with a return condenser with 29 grams of trioxymethylene for3 hours at a temperature of 115 cent. Then ams of colophonium are addedto the still soft resin melt and the mass is condensed further for 4.hours. Lastly the return condenser is removed, and the mass is heated,While stirring, for 2'hours to 210 cent. untilall volatile parts and thewater have been removed v as far as possible. A yellowish resin isobtained, melting at 155 to 195 cent. and

soluble as that obtained by Example 1.

3. 95 grams of pure carbolic acid (commercial). are heated for threehours in a vessel-with a return condenser with grams of formaldehyde of40 weight percents and with 0.2 gram of hydrochloric acid to atemperature of-'110112 cent. To the reaction mixture are then added 30grams of Manila copal andthe Whole is then condensed further for sixhours. a After the water has been removed, the resin mixture obtained isfreed in 2 hours at a temperature of 210 cent. of the volatilecomponents, and will then melt at 135165 cent. The solubility is thesame as that of resin No. 1 and'2, but more easily in linseedoil.

1. 108 grams of cresol, 30 grams of turpentine resin and 28 grams of.paraformal- .dehyde are heated for 6 hours at 115 to 120 cent. To thethus obtained yellow resin 50 grams of kauri-resin are added in smallpieces and the whole is then heated while stirring and removing thevolatile parts and the water, for two hours at a temperature of 250cent. The resin obtained fully equals melted out kauri-resin, melts at160205' cent, and has the same solubility as fossil copals.

Having now described my invention what I claim and desire to secure byLetters Pat ent of the United States is:

1. The process of making phenol-formaldehyde resins soluble in oil whichconsists in combining in a molten state the phenolformaldehyde resinswith natural resins until the mass thus obtained has become soluble infatty oils and oil of turpentine.

2. The process of making phenol-formaldehyde resins easily soluble inoil consisting 1n treating the condensation products of a phenol withformaldehyde and with agents which are soluble both in the producedphenol-formaldehyde-resins and in fatty oils until the mass thusobtained has become fairly soluble in fatty oils. 7,

3. The process of making phenol-formaldehyde resins soluble in oilconsisting in phenol-formaldehyde resins being molten together withnatural resins during so long a period that the mass obtained therebywill easily dissolve in fatty oils.

4. The process of producing phenol-formaldehyde resins consistingincondensing phenol with a formaldehyde substance and melting the thusobtained condensation product with a natural resin in such a quantityand during such a period that the mass oils.

5. The process of making phenol-formaldehyde resins soluble in oilconsisting in the phenol-formaldehyde resinsbeing fused to gether withfossil natural resins.

6. The process of making phenol-formaldehyde resins soluble in oilconsisting in fusing together the phenol-formaldehyde resins with copal.

7. The process of making phenol-formaldehyde resins soluble in oilconsisting in treating the'condensation products of a phenol withformaldehyde and with agents obtained thereby will easily dissolve infatty substance and adding an agent which is solu-' 10 ble both inphenol-formaldehyde resins and in fatty oils and dissolving the productthus obtained in a fatty oil.

In testimony whereof I have hereunto set w my hand in presence of tWosubscribing Witnesses.

LUDWIG BEREND.

Witnesses:

MoRITz WETZEL, MARIA HAHN.

